US5635471A - Odorants - Google Patents
Odorants Download PDFInfo
- Publication number
- US5635471A US5635471A US08/398,726 US39872695A US5635471A US 5635471 A US5635471 A US 5635471A US 39872695 A US39872695 A US 39872695A US 5635471 A US5635471 A US 5635471A
- Authority
- US
- United States
- Prior art keywords
- formula
- mixture
- diastereoisomer mixture
- pure form
- odorant
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
- Expired - Lifetime
Links
- 239000003205 fragrance Substances 0.000 title claims abstract description 10
- 239000000203 mixture Substances 0.000 claims abstract description 30
- 238000000034 method Methods 0.000 claims abstract description 6
- 125000003384 isochromanyl group Chemical group C1(OCCC2=CC=CC=C12)* 0.000 claims abstract description 4
- 238000006798 ring closing metathesis reaction Methods 0.000 claims abstract description 4
- WSFSSNUMVMOOMR-UHFFFAOYSA-N Formaldehyde Chemical compound O=C WSFSSNUMVMOOMR-UHFFFAOYSA-N 0.000 claims description 6
- 239000002253 acid Substances 0.000 claims description 3
- 239000003054 catalyst Substances 0.000 claims description 3
- 238000004519 manufacturing process Methods 0.000 claims 1
- 101100386054 Saccharomyces cerevisiae (strain ATCC 204508 / S288c) CYS3 gene Proteins 0.000 abstract 1
- 101150035983 str1 gene Proteins 0.000 abstract 1
- VLKZOEOYAKHREP-UHFFFAOYSA-N n-Hexane Chemical compound CCCCCC VLKZOEOYAKHREP-UHFFFAOYSA-N 0.000 description 6
- NBIIXXVUZAFLBC-UHFFFAOYSA-N Phosphoric acid Chemical compound OP(O)(O)=O NBIIXXVUZAFLBC-UHFFFAOYSA-N 0.000 description 4
- DHKHKXVYLBGOIT-UHFFFAOYSA-N acetaldehyde Diethyl Acetal Natural products CCOC(C)OCC DHKHKXVYLBGOIT-UHFFFAOYSA-N 0.000 description 4
- VSCWAEJMTAWNJL-UHFFFAOYSA-K aluminium trichloride Chemical compound Cl[Al](Cl)Cl VSCWAEJMTAWNJL-UHFFFAOYSA-K 0.000 description 4
- 239000002904 solvent Substances 0.000 description 3
- YBYIRNPNPLQARY-UHFFFAOYSA-N 1H-indene Chemical compound C1=CC=C2CC=CC2=C1 YBYIRNPNPLQARY-UHFFFAOYSA-N 0.000 description 2
- RTZKZFJDLAIYFH-UHFFFAOYSA-N Diethyl ether Chemical compound CCOCC RTZKZFJDLAIYFH-UHFFFAOYSA-N 0.000 description 2
- OFBQJSOFQDEBGM-UHFFFAOYSA-N Pentane Chemical compound CCCCC OFBQJSOFQDEBGM-UHFFFAOYSA-N 0.000 description 2
- 150000001241 acetals Chemical class 0.000 description 2
- 125000001931 aliphatic group Chemical group 0.000 description 2
- 229910000147 aluminium phosphate Inorganic materials 0.000 description 2
- 229940045348 brown mixture Drugs 0.000 description 2
- 125000004432 carbon atom Chemical group C* 0.000 description 2
- 238000002425 crystallisation Methods 0.000 description 2
- 230000008025 crystallization Effects 0.000 description 2
- ZSIAUFGUXNUGDI-UHFFFAOYSA-N hexan-1-ol Chemical compound CCCCCCO ZSIAUFGUXNUGDI-UHFFFAOYSA-N 0.000 description 2
- 239000000047 product Substances 0.000 description 2
- 239000000126 substance Substances 0.000 description 2
- ONKNPOPIGWHAQC-JHJMLUEUSA-N (4s)-4,6,6,7,8,8-hexamethyl-1,3,4,7-tetrahydrocyclopenta[g]isochromene Chemical compound C1OC[C@@H](C)C2=C1C=C1C(C)(C)C(C)C(C)(C)C1=C2 ONKNPOPIGWHAQC-JHJMLUEUSA-N 0.000 description 1
- ZCMKNGQFIXAHLP-UHFFFAOYSA-N 1,1,2,3,3-pentamethyl-2h-indene Chemical compound C1=CC=C2C(C)(C)C(C)C(C)(C)C2=C1 ZCMKNGQFIXAHLP-UHFFFAOYSA-N 0.000 description 1
- 229910015844 BCl3 Inorganic materials 0.000 description 1
- 241000402754 Erythranthe moschata Species 0.000 description 1
- 238000005727 Friedel-Crafts reaction Methods 0.000 description 1
- 239000002841 Lewis acid Substances 0.000 description 1
- 229930040373 Paraformaldehyde Natural products 0.000 description 1
- GOOHAUXETOMSMM-VKHMYHEASA-N S-propylene oxide Chemical compound C[C@H]1CO1 GOOHAUXETOMSMM-VKHMYHEASA-N 0.000 description 1
- 101150108015 STR6 gene Proteins 0.000 description 1
- 229910003074 TiCl4 Inorganic materials 0.000 description 1
- 229910021623 Tin(IV) bromide Inorganic materials 0.000 description 1
- 229910021627 Tin(IV) chloride Inorganic materials 0.000 description 1
- 238000006243 chemical reaction Methods 0.000 description 1
- 239000013065 commercial product Substances 0.000 description 1
- 239000012043 crude product Substances 0.000 description 1
- -1 dihexyl acetal Chemical class 0.000 description 1
- 125000000118 dimethyl group Chemical group [H]C([H])([H])* 0.000 description 1
- 239000000796 flavoring agent Substances 0.000 description 1
- 235000019634 flavors Nutrition 0.000 description 1
- 150000008282 halocarbons Chemical class 0.000 description 1
- 239000005457 ice water Substances 0.000 description 1
- 238000011065 in-situ storage Methods 0.000 description 1
- HEBMCVBCEDMUOF-UHFFFAOYSA-N isochromane Chemical compound C1=CC=C2COCCC2=C1 HEBMCVBCEDMUOF-UHFFFAOYSA-N 0.000 description 1
- 150000007517 lewis acids Chemical class 0.000 description 1
- 238000002844 melting Methods 0.000 description 1
- 230000008018 melting Effects 0.000 description 1
- 229920002866 paraformaldehyde Polymers 0.000 description 1
- 239000002304 perfume Substances 0.000 description 1
- 239000011541 reaction mixture Substances 0.000 description 1
- 230000000707 stereoselective effect Effects 0.000 description 1
- 230000002194 synthesizing effect Effects 0.000 description 1
- LTSUHJWLSNQKIP-UHFFFAOYSA-J tin(iv) bromide Chemical compound Br[Sn](Br)(Br)Br LTSUHJWLSNQKIP-UHFFFAOYSA-J 0.000 description 1
- HPGGPRDJHPYFRM-UHFFFAOYSA-J tin(iv) chloride Chemical compound Cl[Sn](Cl)(Cl)Cl HPGGPRDJHPYFRM-UHFFFAOYSA-J 0.000 description 1
- XJDNKRIXUMDJCW-UHFFFAOYSA-J titanium tetrachloride Chemical compound Cl[Ti](Cl)(Cl)Cl XJDNKRIXUMDJCW-UHFFFAOYSA-J 0.000 description 1
- JOXIMZWYDAKGHI-UHFFFAOYSA-N toluene-4-sulfonic acid Chemical compound CC1=CC=C(S(O)(=O)=O)C=C1 JOXIMZWYDAKGHI-UHFFFAOYSA-N 0.000 description 1
- FAQYAMRNWDIXMY-UHFFFAOYSA-N trichloroborane Chemical compound ClB(Cl)Cl FAQYAMRNWDIXMY-UHFFFAOYSA-N 0.000 description 1
Classifications
-
- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07D—HETEROCYCLIC COMPOUNDS
- C07D311/00—Heterocyclic compounds containing six-membered rings having one oxygen atom as the only hetero atom, condensed with other rings
- C07D311/02—Heterocyclic compounds containing six-membered rings having one oxygen atom as the only hetero atom, condensed with other rings ortho- or peri-condensed with carbocyclic rings or ring systems
- C07D311/94—Heterocyclic compounds containing six-membered rings having one oxygen atom as the only hetero atom, condensed with other rings ortho- or peri-condensed with carbocyclic rings or ring systems condensed with rings other than six-membered or with ring systems containing such rings
-
- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
- C07C33/00—Unsaturated compounds having hydroxy or O-metal groups bound to acyclic carbon atoms
- C07C33/34—Monohydroxylic alcohols containing six-membered aromatic rings and other rings
-
- C—CHEMISTRY; METALLURGY
- C11—ANIMAL OR VEGETABLE OILS, FATS, FATTY SUBSTANCES OR WAXES; FATTY ACIDS THEREFROM; DETERGENTS; CANDLES
- C11B—PRODUCING, e.g. BY PRESSING RAW MATERIALS OR BY EXTRACTION FROM WASTE MATERIALS, REFINING OR PRESERVING FATS, FATTY SUBSTANCES, e.g. LANOLIN, FATTY OILS OR WAXES; ESSENTIAL OILS; PERFUMES
- C11B9/00—Essential oils; Perfumes
- C11B9/0069—Heterocyclic compounds
- C11B9/0073—Heterocyclic compounds containing only O or S as heteroatoms
- C11B9/008—Heterocyclic compounds containing only O or S as heteroatoms the hetero rings containing six atoms
-
- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
- C07C2602/00—Systems containing two condensed rings
- C07C2602/02—Systems containing two condensed rings the rings having only two atoms in common
- C07C2602/04—One of the condensed rings being a six-membered aromatic ring
- C07C2602/08—One of the condensed rings being a six-membered aromatic ring the other ring being five-membered, e.g. indane
Definitions
- the invention is concerned with a novel odorant, namely the 7R/7S-diastereoisomer mixture of the formula ##STR3## in pure form, wherein "S" indicates that the diastereoisomers are in the S-configuration at position 4.
- the invention also concerns the 2R/2S-diastereoisomer mixture of the formula ##STR4## in pure form.
- the invention concerns odorant compositions containing I and the use of I as an odorant.
- the process involves subjecting the 2R/2S-diastereoisomer mixture of the formula ##STR8## to an isochromane ring closure.
- the invention concerns odorant compositions containing I and the use of I as an odorant.
- the isochromane ring closure of II is preferably carried out using formaldehyde or a synthetic analogue thereof, e.g. the acetal, especially the dimethyl or diethyl acetal or also dihexyl acetal.
- formaldehyde or a synthetic analogue thereof e.g. the acetal, especially the dimethyl or diethyl acetal or also dihexyl acetal.
- Temperature preferably lies between about 0° C. and about 200° C., most preferably between about 85° C. and about 150° C..
- Catalyst a protonic acid, for example p-toluenesulphonic acid or phosphoric acid, etc.
- Acid concentration 1 to 100% (wt./wt.) of the amount of II:
- the acetal can also be prepared in situ from CH 2 O and a lower alkanol.
- Lewis acid especially AlCl 3 , but also SnCl 4 , SnBr 4 , TiCl 4 , BCl 3 , etc.
- Temperature range about -30° C. for about +30° C., especially about -20° C. for about -0° C.
- Solvent saturated aliphatic, optionally halogenated hydrocarbon, for example pentane or hexane, etc., but also the usual, optionally halogenated aromatics, or also CS 2 .
- Ratio solvent to III about 1:10 to about 10:1.
- Ratio catalyst:IV about 1:1 to about 2:1.
- Ratio Ill:IV about 1:1 to about 10:1.
- the diastereoisomer mixture I has very surprising properties.
- mixture I in pure form thus serves in the present case to distinguish this mixture I from the commercial product of formula I' above. It is intended to encompass not only the isolated 7R/7S-diastereoisomer mixture of the formula ##STR11## but, in addition, mixtures that are essentially free of the mixture of (4 R)-isomers found in I', i.e. wherein the (4R)-isomers are present in only minor amount.
- the mixture I can be used as an odorant in exactly the same manner as the known isochromane musk substance, the indene I', although corresponding to the above olfactory threshold values only much lower concentrations of I would be required.
- the crude product was first distilled at 180°--200° C. and at 0.1 mm Hg, and then purified further by crystallization, namely by crystallization from hexane.
Abstract
The invention is concerned with the 7R/7S-diastereoisomer mixture of the formula ##STR1## in pure form, essentially free of the corresponding (4R)-isomers. The invention also concerns the 2R/2S-diastereoisomer mixture of the formula ##STR2## in pure form which is useful as an intermediate for producing I. In addition, the invention concerns a process for obtaining I by subjecting II to isochromane ring closure. Odorant compositions containing I and the use of I as an odorant are also described.
Description
The invention is concerned with a novel odorant, namely the 7R/7S-diastereoisomer mixture of the formula ##STR3## in pure form, wherein "S" indicates that the diastereoisomers are in the S-configuration at position 4. The invention also concerns the 2R/2S-diastereoisomer mixture of the formula ##STR4## in pure form.
Additionally, the invention concerns odorant compositions containing I and the use of I as an odorant.
The mixture of two racemates of the formula I', below, is commercially available. ##STR5## see S. Arctander, Perfume and Flavor Chemicals I, Montclair, N.J. 1969, item 1581. As is apparent from the structure of I', there are asymmetric carbon atoms at positions 4 and 7. Since the structure can be either in the R- or S- configuration at each of the asymmetric carbon atoms, there are four diastereoisomers corresponding to formula I' in the known commercially available mixture.
In accordance with the invention, a stereoselective process has been found for synthesizing the 7R/7S-diastereoisomer mixture of the formula ##STR6## in pure form, wherein "S" indicates that the diastereoisomers are in the S-configuration at position 4. The invention also concerns the 2R/2S-diastereoisomer mixture of the formula ##STR7## in pure form which is useful as an intermediate for producing I.
The process involves subjecting the 2R/2S-diastereoisomer mixture of the formula ##STR8## to an isochromane ring closure.
Additionally, the invention concerns odorant compositions containing I and the use of I as an odorant.
Mixture I is accessible according to the following Scheme: ##STR9##
The isochromane ring closure of II is preferably carried out using formaldehyde or a synthetic analogue thereof, e.g. the acetal, especially the dimethyl or diethyl acetal or also dihexyl acetal. The reaction conditions are as follows:
Temperature: preferably lies between about 0° C. and about 200° C., most preferably between about 85° C. and about 150° C..
Catalyst: a protonic acid, for example p-toluenesulphonic acid or phosphoric acid, etc.
Acid concentration: 1 to 100% (wt./wt.) of the amount of II:
Ratio II:CH2 O: about 0.1-about 1.
The acetal can also be prepared in situ from CH2 O and a lower alkanol.
Conditions which are well-known also apply to the Friedel-Crafts reaction of III to II, for example:
Lewis acid: especially AlCl3, but also SnCl4, SnBr4, TiCl4, BCl3, etc.
Temperature range: about -30° C. for about +30° C., especially about -20° C. for about -0° C.
Solvent: saturated aliphatic, optionally halogenated hydrocarbon, for example pentane or hexane, etc., but also the usual, optionally halogenated aromatics, or also CS2.
Ratio solvent to III: about 1:10 to about 10:1.
Ratio catalyst:IV: about 1:1 to about 2:1.
Ratio Ill:IV about 1:1 to about 10:1.
Working up: addition of an alkanol or aliphatic ether or also mixtures of such solvents, etc. to the reaction mixture. Unless otherwise indicated, ratios are expressed as molar ratios.
The diastereoisomer mixture I has very surprising properties.
Compared with the commercial mixture of the two racemates of the formula ##STR10## its use is very much preferred, which will be immediately evident from the following comparison of all corresponding olfactory threshold values:
______________________________________
(4S)-cis isomer
0.3 ng/l air I (b)
(4S)-trans isomer
0.6 ng/l air I (a)
(4R)-cis isomer
200 ng/l air I'
(4R)-trans isomer
400 ng/l air.
______________________________________
On the other hand, the corresponding value for I' is 1.7 ng/l.
By using I, entrainment of about 50%. of unnecessary and completely functionless ballast is avoided in all cases. The term "mixture I in pure form" thus serves in the present case to distinguish this mixture I from the commercial product of formula I' above. It is intended to encompass not only the isolated 7R/7S-diastereoisomer mixture of the formula ##STR11## but, in addition, mixtures that are essentially free of the mixture of (4 R)-isomers found in I', i.e. wherein the (4R)-isomers are present in only minor amount.
In other respects, the mixture I can be used as an odorant in exactly the same manner as the known isochromane musk substance, the indene I', although corresponding to the above olfactory threshold values only much lower concentrations of I would be required.
a) 7.5 g of AlCl3 were added to a solution, cooled to -10° C., of 26.2 g of 1,1,2,3,3-pentamethylindane in 15 ml of CS2 to yield a yellow-brown mixture. 2.4 g of S (-)-propylene oxide dissolved in 2.5 ml of CS2 were then slowly added to the yellow-brown mixture at -5° C. to -3° C. After completion of the addition the mixture was stirred at 0° C. for a further 30 minutes and then added to ice-water. Working up was effected by taking up in a mixture of hexane-tert.butyl methyl ether in the ratio 1:1.
The crude product was first distilled at 180°--200° C. and at 0.1 mm Hg, and then purified further by crystallization, namely by crystallization from hexane.
The melting point of the product (2S,2'R,S)-2-1',1',2',3',3'-pentamethylindan-5'-yl-propan-1-ol was 73°-74° C., [a]D 22 (C2 H5 OH, c=1.0)-6.23°.
b) The 2-indan-5'-yl-propan-1-ol obtained under a) was treated with paraformaldehyde, 1-hexanol and phosphoric acid exactly according to the procedure of Example 2 of U.S. Pat. No. 3,910,984 and the product, namely (4S,7RS)-1,3,4,6,7,8-hexahydro-4,6,6,7,8,8-hexamethyl-cyclopenta[g]-2-benzopyran, was obtained in good yield. [a]D 22 (C2 H5 OH, c=1.18)+21.4°.
Claims (4)
1. A 7R/7S-diastereoisomer mixture of the formula ##STR12## in pure form, essentially free of the corresponding (4R)-isomers.
2. A 2R/2S-diastereoisomer mixture of the formula ##STR13## in pure form.
3. An odorant composition, which contains the diastereoisomer mixture of formula I according to claim 1.
4. A process for the manufacture of the diastereoisomer mixture of formula I according to claim 1, which process comprises subjecting a 2R/2S-diastereoisomer mixture of the formula ##STR14## to an isochromane ring closure by means of formaldehyde or a synthetic analog thereof in the presence of a protonic acid as catalyst at temperatures between 0° C. and 200° C.
Applications Claiming Priority (2)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CH70894 | 1994-03-10 | ||
| CH708/94 | 1994-03-10 |
Publications (1)
| Publication Number | Publication Date |
|---|---|
| US5635471A true US5635471A (en) | 1997-06-03 |
Family
ID=4193322
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| US08/398,726 Expired - Lifetime US5635471A (en) | 1994-03-10 | 1995-03-06 | Odorants |
Country Status (6)
| Country | Link |
|---|---|
| US (1) | US5635471A (en) |
| EP (1) | EP0677521B1 (en) |
| JP (1) | JPH07258244A (en) |
| DE (1) | DE59508616D1 (en) |
| ES (1) | ES2150999T3 (en) |
| SG (1) | SG69962A1 (en) |
Cited By (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US20040157764A1 (en) * | 2003-02-10 | 2004-08-12 | Sprecker Mark A. | Solid phase benzopyran composition, process for preparing same and organoleptic uses thereof |
Citations (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US3910984A (en) * | 1972-11-27 | 1975-10-07 | Plantex Ltd | Benzylcyano-amides |
| US4162256A (en) * | 1978-04-19 | 1979-07-24 | International Flavors & Fragrances Inc. | Process for the production of compounds useful in perfumery |
| US5376630A (en) * | 1994-03-17 | 1994-12-27 | International Flavors & Fragrances Inc. | Methyl, substituted propyl-substituted pentamethyl indane derivatives, processes for producing same and perfumery uses thereof |
Family Cites Families (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US3660311A (en) * | 1970-01-09 | 1972-05-02 | Int Flavors & Fragrances Inc | Novel fragrance methods and compositions |
| GB1476925A (en) * | 1973-08-23 | 1977-06-16 | Unilever Ltd | Oral preparations |
-
1995
- 1995-02-22 SG SG1996004400A patent/SG69962A1/en unknown
- 1995-02-22 EP EP95102462A patent/EP0677521B1/en not_active Expired - Lifetime
- 1995-02-22 DE DE59508616T patent/DE59508616D1/en not_active Expired - Fee Related
- 1995-02-22 ES ES95102462T patent/ES2150999T3/en not_active Expired - Lifetime
- 1995-03-06 US US08/398,726 patent/US5635471A/en not_active Expired - Lifetime
- 1995-03-09 JP JP7050005A patent/JPH07258244A/en active Pending
Patent Citations (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US3910984A (en) * | 1972-11-27 | 1975-10-07 | Plantex Ltd | Benzylcyano-amides |
| US4162256A (en) * | 1978-04-19 | 1979-07-24 | International Flavors & Fragrances Inc. | Process for the production of compounds useful in perfumery |
| US5376630A (en) * | 1994-03-17 | 1994-12-27 | International Flavors & Fragrances Inc. | Methyl, substituted propyl-substituted pentamethyl indane derivatives, processes for producing same and perfumery uses thereof |
Non-Patent Citations (1)
| Title |
|---|
| S. Arctander, Perfume and Flavor Chemicals I, item 1581, (Montclair, NJ, 1969). * |
Cited By (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US20040157764A1 (en) * | 2003-02-10 | 2004-08-12 | Sprecker Mark A. | Solid phase benzopyran composition, process for preparing same and organoleptic uses thereof |
| US7407928B2 (en) | 2003-02-10 | 2008-08-05 | International Flavors & Fragrances Inc. | Solid phase benzopyran composition, process for preparing same and organoleptic uses thereof |
Also Published As
| Publication number | Publication date |
|---|---|
| EP0677521A1 (en) | 1995-10-18 |
| SG69962A1 (en) | 2000-01-25 |
| EP0677521B1 (en) | 2000-08-09 |
| DE59508616D1 (en) | 2000-09-14 |
| ES2150999T3 (en) | 2000-12-16 |
| JPH07258244A (en) | 1995-10-09 |
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Legal Events
| Date | Code | Title | Description |
|---|---|---|---|
| AS | Assignment |
Owner name: GIVAUDAN-ROURE (INTERNATIONAL) SA, SWITZERLAND Free format text: ASSIGNMENT OF ASSIGNORS INTEREST;ASSIGNORS:FRATER, GEORG;MULLER, URS;PETRZILKA, MARTIN;REEL/FRAME:007438/0426;SIGNING DATES FROM 19950224 TO 19950227 Owner name: GIVAUDAN-ROURE CORPORATION, NEW JERSEY Free format text: ASSIGNMENT OF ASSIGNORS INTEREST;ASSIGNOR:GIVAUDAN-ROURE (INTERNATIONAL) SA;REEL/FRAME:007445/0069 Effective date: 19950228 |
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| AS | Assignment |
Owner name: GIVAUDAN-ROURE (INTERNATIONAL) SA, A SWISS COMPANY Free format text: ASSIGNMENT OF ASSIGNORS INTEREST;ASSIGNOR:GIVAUDAN-ROURE CORPORATION;REEL/FRAME:008283/0369 Effective date: 19961211 |
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